There is a continuing search for materials having desirable fragrance properties. Such materials are sought either to replace costly natural materials or to provide new fragrances or perfume types which have not heretofore been available. Especially desirable qualities for substances having interesting hyacinth fragrances, or narcisse fragrances, or violet fragrances, or oriental vetivert fragrances, or otto of rose fragrances are stability and persistance, particularly in a wide variety of perfumed articles (e.g., soaps, detergents and powders), perfume compositions and colognes, ease of manufacture and intensity of aroma.
Prior to this last decade it was the general opinion among those skilled in the art that compounds containing the mercapto or --SH moiety or substituted mercapto or --SR moiety (where R is an organic group such as alkyl or acetyl) were not desirable for use in conjunction with fragrance materials and perfumed articles such as soaps, detergents and powders. However, within the last decade such compounds have been ascertained to be highly useful in perfumery.
Thus, for example, British Pat. No. 1,423,914 and 1,423,915 issued on Feb. 4, 1976, teach that certain mercapto derivatives which are aliphatic or cycloaliphatic compounds having the formula: ##STR4## wherein X' represents a hydroxyl group or an acyloxy group, and X.sup.2 represents a hydrogen atom; R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom or a univalent aliphatic hydrocarbyl group; or R.sup.1 and R.sup.3 or R.sup.4, together with the intervening carbon atoms, constitute a cycloaliphatic ring, are useful as perfuming agents as exemplified by adding 3-methylthio-hexanol to a perfume base composition of the "Fleuri" type wherein the 3-methylthio-hexanol is said to give rise to a green, fruity aroma reminiscent of that of rhubarb.
Furthermore, for example, Canadian Pat. No. 983,050 issued on Feb. 3, 1976, teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol) of the formula: ##STR5## is used in making up a "synthetic buchu lead oil" and imparts to a lavender type composition a greener and more herbal fragrance. USSR Pat. No. 345,677 teaches that para-menthane-8-thiol-3-one is useful as a synthetic black currant flavoring for foodstuffs. This compound has the structure: ##STR6## German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973 discloses the use of certain thio alcohols or their corresponding esters in perfumery and in perfumed articles, such as detergents, cosmetics and waxes. Such mercapto alcohols having the generic structure: ##STR7## wherein R.sub.1 is a hydrocarbon moiety having from 1 up to 7 carbon atoms and R.sub.2 is one of hydrogen, methyl or ethyl.
U.S. Pat. Nos. 3,950,429 issued on Apr. 13, 1976, and 3,952,062 issued on Apr. 20, 1976, disclose certain alkylthiosubstituted oxo-terpenoids having 10 carbon atms in the terpenoid skeleton as useful in perfumery and in flavors, particularly for providing vegetable notes. The generic structure of the compounds is as follows: ##STR8## wherein
R.sup.1 represents hydrogen or together with R.sup.4 represents a C--C bond,
R.sup.2 represents hydrogen or together with R.sup.6 represents a dimethylmethylene group, or, when R.sup.6 is isopropyl, together with R.sup.5 represents a C C bond,
R.sup.3 represents hydrogen or together with R.sup.6 represents a dimethylmethylene group,
R.sup.4 represents hydrogen or together with R.sup.1 represents a C C bond,
R.sup.5 represents hydrogen or, when R.sup.6 signifies isopropyl, together with R.sup.2 represents a C C bond,
R.sup.6 represents isopropyl or together with R.sup.2 or with R.sup.3 represents a dimethylmethylene group,
R.sup.7 represents methyl,
X represents a C C double bond taking the place of a C C single bond,
m = 0 to 2,
Y represents oxo bound to a primary or secondary C-atom and Z represents mercapto or lower alkylthio located in the .beta.-position to the carbonyl function,
provided that when R.sup.2, R.sup.3 and R.sup.5 represent hydrogen, R.sup.6 represents isopropyl, R.sup.4 together with R.sup.1 represents a C C bond, Y is .beta. to the carbon atom bearing the substituent R.sup.7, m=o, Z is .alpha. to the carbon atom bearing the substituent R.sup.5 and .beta. to the carbon atom bearing the substituent R.sup.3 then Z represents alkylthio.
However, none of the disclosure of the prior art contains a teaching to the effect that compounds having the generic structure: ##STR9## wherein R is one of methyl or hydrogen; X is one of ##STR10## and Y is one of methyl, methallyl having the structure: ##STR11## n-propyl, 2-methyl-1-propyl or acetyl, has the ability to create an intense sweet and/or green and/or floral and/or herbal and/or vegetative and/or basil-like and/or minty and/or melony and/or grapefruit and/or fruity and/or alliaceous aroma with yara and/or neroli and/or verdima nuances as is carried out using the instant invention. Furthermore, other substituted mercaptans in the prior art which are shown to be useful in perfumery and other mercaptans in the prior art which are shown to be useful in perfumery are indicated to have rhubarb-like or berry or other type floral fragrances, e.g., ionone and irone derivatives having the structure: ##STR12## as disclosed in British Pat. No. 1,327,320, published on Aug. 22, 1973, wherein one of the dashed lines represents a double bond, and where R is hydrogen or alkyl.
Certain .alpha.-oxomercaptoalkanes are disclosed in the prior art, but their uses in perfumery, in perfumed articles or in colognes are not disclosed. Thus, U.S. Pat. No. 3,773,524, issued on Nov. 20, 1973, discloses the use of .alpha.-ketothiols of the formula: ##STR13## wherein R.sub.1 is methyl or ethyl; and R.sub.2 and R.sub.3 are hydrogen, methyl or ethyl to alter the meat flavor and aroma of foodstuffs. U.S. Pat. No. 3,892,878, issued on July 1, 1975, discloses the use of certain .alpha.-hydroxymercaptoalkanes to alter the flavor of foodstuffs, for example, 2-mercapto-3-butanol used in meat flavors. The genus disclosed by U.S. Pat. No. 3,892,878 is as follows: ##STR14## wherein X is oxygen or sulfur, n is 0 or 1, R.sub.1 -R.sub.7 are the same or different and each is hydrogen or lower alkyl of 1-4 carbon atoms, a and b are the same or different and each represents an integer of from 0 to 10 when n is 0 and when n is 1, a and b are the same or different annd each represents an integer of from 1 to 10.3-mercaptoheptanone-4 is disclosed per se in U.S. Pat. No. 2,888,487, issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one is disclosed in Chem. Abstracts 6478 (d) Vol 62, 1965 (abstract of Asinger, Diem and Schaefer, Monatsh, Chem, 95 (4-5), 1335-54 (1964). Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-on page 4039, 1-mercapto-octan-2-on at page 4040; and 1 -mercapto-nonan-2-on at 4052 and 1-mercapto-undecan-2-one at page 4060.
U.S. Pat. No. 3,922,366 issued on Nov. 25, 1975, discloses the enhancemennt of foodstuffs by addition of a small but effective flavor modifying amount of a compound of the general formula: ##STR15## wherein R.sub.1 is hydrogen or alkyl and R.sub.2 is alkyl or furfuryl. The flavor nuances where are enhanced or altered are those which are found in coffee flavors and aromas.